Process of treating fatty material



May 23, 1944. H. o. RENNER PROCESS OF TREATING FATTY MATERIALS Filed Jan. 10, 1940 4 Sheets-Sheet 1 ESS May 23, 1944- n H. o. RENNER 2,349,377

PROCESSA OF TREATING FATTY MATERIALS Filed Jan. 10, 1940 4 Sheets-Sheet 2 May23,1944. H Q, RENNER `2,349,377'

PROCESS OF TREATING FATTY MATERIALS Y Filed Jan.` 1o, 1940 4 sheets-sheet s My 23, 1944. H. o. RENNER 2,349,377

PROGESSDF TREATING ATTY MATERIALS Patented May 23, 1944 rnocnss or Tammo ra'rrr MATERIAL Herbert Otto Renner, Des Plaines, Ill., assigner, by mesne assignments, to J. R. Short Milling Company, Chicago, lll., a corporation of Illinois Application January 10, 1940, Serial No. 313,284 7 claims. (ci. sis-11S) This invention relates to improvements in processes of treating fatty material including edible oils "and fats or mixtures thereof, and to products resulting from such processes. More particularly, the invention relates to the treat-v ment of fatty acid compositions such as vegetable and animal glycerides of fatty acids and the fatty acids themselves to prevent the development of undesirable odors or avors therein. In the treatment of edible fats and oils by various processes applied prior to their -use in foods or in other commodities where flavor or odor are important considerations, products obtained may at tim'es contain certain constituents that have undesirable odors and flavors or constituents from which such odors or flavors are developed even after the use of such products in, for instance, foods such as baked or other goods. The undesirable odors and flavors may be ascribed to various factors and to the presence of various substances initially in the fats and oils or to substances formed as a result of some chemical reaction.

`The object of the present invention is to provide a process for effectively improving an oil or fat and for treating oils and fats by subjecting the oils or fats to a preliminary modifying treatment. The problem will first be ydiscussed from a process standpoint and thereafter suitable apparatus for effecting the process will be described.

Particularly useful results are obtained by pretreating oils and fats processed in accordance with the inventions described and claimed in application `Serial No. 127,308, filed February 23, 1937, and Patent No. 1,994,992, to L. W. Haas and H. O. Renner, and in application Serial No. 245,502, led December 13, 1938. TheV processes described in the above application Serial No. 127,308 and Patent 1,994,992; are for the purpose of prep ring oxidized oils or fats suitable for use in basing processes primarily for bleaching purposes. oxidation processes, an animal or vegetable oil or fat'is agitated vigorously in the presence of enzyme extracts and in the presence of air, oxygen, or other gas containing free oxygen at a temperature between 32 and 140 F. or preferably 70 to 78F. for a period depending on the extent of oxidation desired. 'I'he enzyme extracts are prepared from legumes such as soybeans containing peroxidizing enzymes, so termed here because of the characteristic of the enzyme active agent such as unheat-treated soy flour. to modify -in the course of a peroxidation treatment, ap-

parently catalytically, thefatty material, so that it may be used in effecting subsequent bleaching of other material, as for example bread dough. The resultant peroxidized oil or fat is separated from the resulting mixture, preferably by means y of a high-speed centrifuge. Such peroxidized oil For instance, in thev or fat has been found to be highly useful in the baking of dough in that it serves both as a short- Vfening agent and as a bleaching agent'for the dough, as disclosed in Patent No. 1,994,993 to L. W. Haas and H. O. Renner.

The above enzyme oxidized oil or fat may be refined to a certain extent by means of a process described and claimed in said application Serial No. 245,502. 'I'he latter application discloses a process in which oils or fats, and especially peroxidized oils or fats having a rancid odor or avor or producing undesirable odors or flavors in baked goods for instance are mixed with water and plasmolyzed yeast, or enzymes obtained from living micro-organisms by plasmolysis, autolysis, maceration, or suitable mechanical means. The mix is constantly and thoroughly agitated, while avoiding aeration, for a relatively short period cordance with the above disclosures or other wellknown processes a highly improved product is obtained. The pre-treatment is carried out as follows:

A-fatty acid composition, such as an edible vegetable or animal oil or fat, a fatty acid, or mixtures thereof, preferably rened in accordance with the ordinary well-known commercial processes, is treated with a relatively small proportion of a halogen in condition to react as desired. The halogen is thoroughly dispersed throughout a body of the fatty material to modify minor constituents thereof which cause the aforementioned undesirable odors and flavors. Such constituents aremore or. less unknown as to their constitution and appear to cause an oil to turn rancid or to impart to baked goods an unpleasant avor.

The fatty material under treatment is not intended to be subjected to an extended halogenation. The glycerides of a fat or oil for instance should not be halogenated. The amount of halogen used in a given quantity of fatty material is preferably just enough to halogenate the- Vsubstances causing rancidication and/or other qualityd constituents are generally present in an oil v'or fat in extremely smallconcentration's, proportionately small amounts of llalogens are lrequired to modify these constituents. Y standpoint it.is impossible to carry ont the present halogen treatment without 'employingv some peratures as, for instance, f'roln 110 to 120 FL, as

a rule tend to affect the stability of oils unfavor ably and should' therefore be preferablyI avoided. At such higher temperatures, the fhalogenation reaction per se does not vdiffer noticeably from the reaction `lit-ordinary temperatures so far the d properties ofthe treated fatty" material is concerned.

From vil. practical n y 4 4 fo?? materialis to be put. Since the aforesaid minor tively dilute as. for instance. a concentration of about 0.3 per cent.

.. Bromine' behaves more nearlylike chlorine than iodine' in the present process'. It may be used excess halogen. The halogenreacts first onthe minor constituents and any excess will react with I the present process.

as 'auch in very minute quantities. Proportions 'of about 0.01 per cent based on the weight of an oil may be employed.

:.Hlogenation with chlorine in the absence of waterl in the present process makes unnecessary @1.1! treatment of afatty material .before subsequent enzyme-oxidation. Chlorination in the presence of water requires an intermediate treat- Temperatures If the viscosity of an oil to be treated permits, l

lower temperatures are preferablyl used since they favorthe desired reaction of the halogensgwith the minor constituents to be modined. The velocity of the reaction :between the glycerides of an oil and a halogen appears t'o decrease with decreasing temperatures, at' a faster rate than I the velocity of the-reaction between sucii'halogen and the more highly reactive minor constituents of theoil. The result appears tolbethat at lower temperatures the 'desired reaction is moreselective and requires less halogen.

By way of illustration, the treatmentq'f fatty material with each of the halogens in accordance specincally below.

At thepreferred temperatures mentioned above",` a refined peanut oil or cottonseed oil, preferably.y

water-free, is thoroughly mixed Awith about 40.05

per cent of dry chlorine based on the weight of the.

oil. The chlorine`is entirely absorbed by the oil.

As high as about 1 per cent of chlorine may be,

absorbed by the oil treated without interference with the subsequent enzymeoxidation of the treated oil and its use in bread baking. Iodine is the least reactive ofthe halogens with f the glycerides, and'in contrast to chlorine and bromme, it may be dissolved .in edible oils up to relatively high concentrations without becoming chemically' united with the glycerides. The fact that excess iodine tends to produce a reddish or pinkish color renders the use of iodine practical from the standpoint of determining' tle proporwith a preferred procedure will beset forth more amountsof a halogen reagent is illustrated in nient. In other words, the acid that is formed, namely.A hydrochloric acid,` must be neutralized and the oil clarined.

:y In` the case of iodation,no intermediate treatment is required whether or not water is present during lthe iodation. Broxnine behaves somewhat similarly to chlorine. In the absence of water no' acid isforlnedv while in thepresence of water. hydrobromic acid is formed. The acid formed is neutralized and the neutralized material may removed by'high-speed centrifuging.

tIn application Serial No. 260,862, filed March 9,1939. of which thepresent application is a continuation in part, `a process of treating fatty` material is set forth in which fatty material, such qsfedlme oils and fais. is mixed with chlorinated lime and then with sulphuric acid tolgenerate a small amount of chlorine in the body of the material to'modify the small amounts of minor relatively unstable constituents therein. In this instance, as soon' as the chlorine freed from the chlorinated lime by the addition of acid is taken up by the oil or fat, anhydrous sodium carbonate or a solution -thereof is added to neutralize all the free' acid present in the mix. After the acid is 'neutralized the treated fatty material is clarified by high-speed centrifuging.

- It is found more highly advantageous inthe vpresent process to introduce an initially free halogen. element into fatty material to obtain the de sired effect. Apparatus that has been found particularly efficient for use in the treatment of liquid fatty materials with small or relatively minute thefaccompanying drawings in which- Fig.' 1 is a side elevation. partly in cross section, of one form of apparatusfor treatment of fatty material with a halogen in relatively smallv proportions: i

-inFig,l;

Fig. 3 is Fig. 2 is a vertical section of a fragment lof a reaction tube employed in the pparatus shown a sectional view of the reaction tube on line 3-3 of Fig. 2:

Fig. 4 is a sectional view ofl the-reaction tube on' lined-4 of Fig. 2 showing a planof an agitator tion of iodine needed to modify the undesirable minor constituents. The' iodine reacts substantiallyfinstantaneously with such constituents without producing any color.'4 Thus the optimum proportions of iodine incorporated in 'an oil may be I determined by gradually adding iodine while no,

change in color of the oil is noticeable. As little as 0.001 per cent of iodine 'based'on the weight of an oil has been found sufilcient to' modifysuch oil in the desired manner. In large-scale manufacturing, approximately '"9' grams of4 iodine is regulator shown in Fig. 1;

eleuient employed in the tube;

` Fig. 5 is a vertical'section of a gas regulator I' means employed in the apparatus shown in Fig.'1;

Figs. 6 and l are fragments partly in section of parts of the gas regulator shown in Figs. 1 and 5:

Fig. 8 is a iront view of a fragment of thegas Fig. 9 is a side elevation partly in section of a modiflcation of apparatus shownin Fig. 1; and '"Iiig. 10 is a flow sheetindicating the several steps of the process of this invention.

found to be suillcient'for'the treatment of f'ton of oil. The iodine is preferablyus'ed in solution.

As high as 18 grams of iodine per tonof 'peanut-oil maybe used. The iodine solution may be rela- 't5 through which oil to be treated is continuously A preferred form of the apparatus for the here- A i? in described halogen treatment, particularly withl chlorine gas', comprises a-reaction tube I (Fig. 1),

stituents of the oil with the reactive chlorine passed at a predetermined rate while agitating in the presence of chlorine, preferably undiluted and pure, fed into the body of the oil at a predetermined rate. The reaction tube is U-shaped and is mounted in a vertical position. 'I'he tube may be yconstructed of cast iron lined with glass. One leg of the tube is provided with means for introducing oil to be treated and with means for introducing chlorine. The other leg serves as an overow which provides for a constant head of cil 4in the tube. 'I'he oil level is shown at 2 in the inlet leg of the reaction tube.

The oil to be treated may be fed into the inlet leg of the reaction? tube I from an oil reservoir (not shown). The oil is fed into the reaction tube at a uniform, predetermined rate by means kof a pump 3. If desired, the rate oi ow may be controlled by a valve 4 as well as by the pump 3. When conditions are maintained uniform at all times as, for instance, when the same oil with uniform characteristics is treated under uniform conditions, the rate of feed of the oil may be xed by the size of the impeller blade of the pump as well as by a control disc having a bore hole of fixed diameter, which is inserted in the feed pipe 5 leading from the pump 3 to the reaction'tube I. The said disc is indicated by the numeral 6 in the oil feed line 5.

The oil feed line 5 passes into the inlet leg of theV reaction tube I through a side' arm 1 adjacent the top of the said inlet leg and above the level at which the oil column is maintained. At the inner end vof the il feed line 5 is a 45 elbow 8 placed in a position for directing the oil d ownwa'rdly and in the direction in which the oil is rotated by an agitator to be described below. The agitator is suspended from a cover plate 9 at thetop of the inletl leg of the reaction tube I. The agitator comprises a rotary shaft I0, a plurality of agitator discs II, and a plurality of deflecting rods I2.

The deilecting rods I2 are held in place by means of suitable connections with the cover plate! and are mounted in stationary position about the agitators II, parallel tothe shaft 'IIL The deflecting rods are spaced from the shaft to permit rotation of the agitators II. A plurality of means I3 are secured to the deilecting rods for supporting a bearing I4 (Fig. 2) for the shaft IB. One such bearing-supporting means I3 is Vshown near the lower end of the shaft I and another adjacent the level of the oil in the reaction tube. The bearing-supporting means I3 are adjustable and are held in place by set screws I (Fig. 3) co-acting with the deiiecting rods I2 and by a set screw I6 co-acting with the shaft I0.

The agitator means II comprises a plate havingperforations I'I (Figl 4). Five such agitator gas can be established, and upon the carrying out of the reaction to a satisfactory point, the agitator s erves as an important element of the apparatus. The agitator shown disperses the gas entering the reaction tube in a finely divided condition and within the shortest possible time so `that it is practically instantaneously completely absorbed by the oil. The deflecting rods I2 coact effectively with the agitator elements II to distribute the gas in the oil.

The chlorine gas is fed into the inlet leg of the reaction tube at a predetermined level below the level 2 of the oil through a pipe 26. The pipe 26 passes through a cover plate 21 aiiixed to the end of a side arm 28 of the reaction tube I. The

Y open end of the pipe 26 is positioned preferably 4I' ofthe said gauge stick 4I.

so as to admit the gas into the body of the oil at a point between two agitator elements II.

The rate of introduction of the chlorine gas may be controlled by a valve 23 in the pipe 26 which leads to a pipe 30 provided with a valve 3|, which in turn is connected to the chlorine gas supply. The pipe 26 also leads to a pipe 32 provided with a valve 33 which in'turn is connected to an inert gas supply. The purpose of the inert gas is to replace chlorine in the pipe lines when found necessary. 'I'he inert gas may be nitrogen. In order to provide for effectively regulating the rate of introduction of chlorine gas into the reaction tube, a gauge unit shown in Figs. 1, 5, 6, and 7 is connected to the pipe 26 by means of a `pipe 3d. The pipe 34 passes downwardly and is connected to a glass tube 34' which extends into a gauge tube 35 to a point slightly above the bottom thereof and below the level of a gauge liquid 36, such as water. The glass tube 34 has its lower end 31 open to permit free passage of liquid or gas therethrough. The gauge tube 35 is provided with a suitable gas-tight cover 38. A passage 39 leading from the interior of the gauge tube 36 is provided -in the cover 36 and is connected to a pipe 40.

To the outside of the gauge tube 35 is attached a gauge stick 4I provided with suitable markings to indicate liquid levels in the gauge `tube and to indicate distances from the top end The gauge stick 4I is' attached at its upper end to a collar 42 which engages the gauge tube 35. The gauge stick is held in place by means of a bolt 44 and a nut 45. The bolt M passes through an enlarged opening 46 in the gauge stick 4I so that the latter may be adjusted vertically. The lower end of the gauge stick 4l is free and permits the movement of a slide 43 along the same.

means are shown in the reaction tube in Fig. 1,

spaced apart and amxed to the shaft In by means of collars I8 and I9 attached to the shaft above and below each of the agitators II, respectively, by means of set screws 20 and2I. The discs II are adjustable and the distances between them may be varied. In the drawing they are shown to be substantially equal distances apart.

A motor 25 is mounted above the plate 9 and attached to the end of the rotary shaft I0. The motor is adapted to rotate the shaft at high speed.` The desired union of the chlorine gas and the oil is accomplished by a rotation of approximately 3,000 R. P. M. Since the effectiveness of the chlorination treatment for the purpose described depends largely on the velocity with which intimate contact of the minor con- It is seen that byV admitting gas into the reaction tube I under a given head of oil, a certain pressure is needed to overcome this head. At the same time the rate of feed of the gas must be properly adjusted in accordance with the rate of passage of oil through the reaction tube so that the gas and oil are properly proportioned. By adjusting the feed of gas so as to maintain the position of the meniscus of the gauge liquid in the tube 34 and the position of the meniscus of the gauge liquid in the gauge tube 35 a proper predetermined distance apart, the propoztion of gas to oil may be regulated as desired.

of the gauge liquid. If the pressure is too great` the oil.

the gauge liquid is forced out of the tube u' and the gas eventually escapes through the pasi sage 39. I

T set the gauge, the top end 4I' of the gaugeV stick 4I is positioned so that during the operation of the apparatus the meniscus of the gauge liquid in the gauge tube 35 is maintained in horlzontal alignment with the top end 4I of the gauge 'stick and of the slidable collar 42. Also A during operation the meniscus of the gauge liquid in the tube 34' iskept in horizontal alignment with the top edge of the gauge slide 43. The distance between the two meniscuses is the equivalent of the head of oil in the reaction tube plus the added pressure required to feed the gas at the desired rate and in proper proportion to By proper calibration this distance mayl be predetermined. During the feed offthe gas,

the gauge is observed from time to time to make certain that the proper lrate of delivery is maintained. If found necessary the pressure of the gas is adjusted by manipulating the valve 3I in the gas feed line 30. v

For the purpose of preventing the escape of chlorine gas into the atmosphere, it has been found advantageous to connect the pipe 40 to an absorber. The absorber comprises a closed tank 41. The pipe 40 is connected to a pipe 43 which extends downwardly through the center of the tank 41- and is provided with an open end 49 which is positioned below a perforated plate l0 above which an absorbent material 5I is placed.

An absorbentmateri'al :that is satisfactory for absorption of chlorine is sodium carbonate, preferably in lump `.form and prefera ly the decahydrate. A drainage hole may be provided in the bottom of the tank,41 in which is placed an overow pipe 52 which prevents clogging of nthe drainage hole by solid crystals that are apt to form during the reaction of the chlorine with the absorbent. During the operation of the apparatus, the drainage hole is kept closed by means of a plug 53. Any gas which accidentally or otherwise passes through the gauge 35 into the tank 41 is' absorbed by the sodium carbonate without influencing the readings on the gauge.

In the operation of the above apparatus, the

reaction tube I is first filled with the oil to be treated by pumping the oil into .the tube by means of the pump ,3. When the level of the oil reaches the level of the overflow pipe, namely,

the level 2, the pump is stopped. The 'agitator motor 25 is then started. The valve 3l in the chlorine feed line 3Il'is gradually opened, valve 2 9 being momentarily kept closed. The chlorine gas passes into the tube 34" and forces the gauge liquid downwardly therein. When the movement of the gauge liquid in the tube 34' indicates that some pressure has been created, the valve 23 is immediately opened. The valve 3l in the chlorine feed line 30 is then adjusted until "the desired operating pressure has been attainedas ofthe gauge liquid in the tube 34' tothe reading indicated bythe slide 43. As soon as the desired pressure is attained, the oil pump is immediately started and the feed of oil maintained at the desired predetermined rate of now. The feed oiI g'as and ,oil is so proportioned that about lpa'rt by weight of chlorine per second .is introduced into the reaction tube for every 1,000 parts by weight of oil passing through the reaction tube in the same period of time. As indicated above,

this proportion may be varied as found necessary.

From time to time byway of precaution, the

. will be observed by the lowering of the meni's'cus Jas-19,377

oil passing out of the reaction tube may be tested for its acidity. If the oil and the chlorine gas are free from moisture upon entering the reaction tube, such acidity is not likely to develop and therefore routine tests are not required.

Whenstopping the operation of the apparatus, the oil pump is stopped and the valve 4 closed: the valve-3l in the pipe 30 is closed to shut oil! the supply of chlorine; the valve 3 3 in the pipe 32 is slowly opened., whereupon 4the inert gas passes through the pipe V26 into the reaction tube I and the feeding thereof is continued until all the chlorine in the variousV pipe connections has been replacedby inertl gas. The valves 33 and- 29 are closed and the agitator i's stopped. The

oil in the reaction tube I may be drained out by removing a drainage plug 55.

In Fig. 9 the means are shown whereby oil'v may be treated with iodine solution inthe proportions indicated above. .The same type of reaction tube as that shown in Fig. 1 may be used and the gas inlet arm 2li may be sealed oi by means of. a plug 56. The iodine solution is l fed into the top of the oil column in the reactiontube I from a container 58 which maybe made of glass and may be graduated as at I3. 'Ihe top section of the inlet leg oi the reaction tube I is provided with two inlet arms GII and 6I, the inlet arm .50 being provided for the introduction of the oil to be treated and the inlet arm 6I being provided for the introduction of the iodine solution.

elbow in the manner described in connection with the apparatus shown in Fig. 1. The con- 'tainer 58 is connected to the reactiontube by means of 'a pipe 32 provided with a control valve 63.' 'I'he open end of the pipe 62 within the reaction tube I is so placed that the iodine solution is delivered directly into the stream of oii entering the said reaction tube. The feed `oi' the oil ando! the iodine solution is so controlled that the iodine and the oil are properly proportioned. The proper proportion of iodine to oil may be roughly indicatedcby the,- color of the treated oil leaving the reaction tube. If uthe treated oil has a very faint pinkish shade;

the proportions may vbe considered proper.

A'complete process for the preparation of a highly improved product for use as a shortening and bleaching agent in the baking of dough, vfor instance, comprises the following steps as shown in the ow sheet shown in Fig. l0:

` 1. The oil is pre-treated with a halogen and` agitated at high speed, they oil and the halogen being fed into a reaction zone 85, in proper proportions.

4.'The fatty material is separated from the agent which provided the enzyme active factor, andthe resulting: fatty product may be usedI as such for bleaching of dough.

5.- If the oil resulting after the treatment by The oil is fed into the reaction tube through the pipe 5 and the.

If ythe resulting mixture contains l acid, it is treated'to neutralizethe acid or remove the same. If the resulting mixture showsmeans of the above steps is liquid at room tem'- parts by Weight of concentrated soy flour extract to supply the enzyme activity (obtained by mixing about 200 parts by weight of enzyme;V active or unheat-treated soy ilour in about 1200 parts by weight of 0.2 per cent calcium chloride solution in water and centrifuging) diluted with about 5000 parts of Water.

'ro the thus catamicany oxidized on coni' tained in the above mixture, about parts by weight of plasmolyzed yeast are added, and these mixed together at 24 C. for about one and one? half hours. The pH during this enzyme renf ing process is maintained at about 6.5 to 7.0 L The renned oil is separated from the resulting mixture by centrituglng, and may be blended with other oils or fats for use in baking or other processes.

In the process of the present invention', a pretreatment is applied to fatty acids or 'fats and oils; and to mixtures thereof, for the purpose' of destroying or modifying certain minor con-` stituents-thereof which are apt to give rise to undesirable odors and flavors in these fatty materials or more particularly to odors and flavors considered undesirable in the products in which4 they are ultimately used. It is found that halogenation of edible refined oils, as described, prior to their use as raw materials for the production of enzyme-activated oils having dough-bleaching properties, results in the complete elimination of the disagreeable odors and objectionable fla` vors which adversely affect the taste appeal of bread in which such oils are used. The process has utility not only in the production of oxidaf tion products and enzyme-treated fatty material' but also in the refining of edible fats and oils in general.

The invention has been disclosed herein for illustrative purposes in its preferred embodiment, but it is to be understood that the scope of the invention is dei-ined by the appended claims rather than by the aforegoing description.

What is claimed ist 1. In a process of treating renned edible oils,

fatty oils and fatty acids, by peroxidation and.

bromine. when @menne is used the amount'being from about 0.05 percent to about 1.00 percent, when iodine is used the amount being from about 0.001 percent to about 0.002 percent, and when bromine is used the amount being about 0.01 percent; each being based on the weight of the fat treatedkthe treatment being conducted withthorough vmixing. so that the contact between the halogen and the fat is such that the halogen acts on those constituents of the fat which other- A ing conducted with4 thorough mixing, so that the wise would produce oil-flavors and oil-odors. the

amount of the halogen being insuillcient to substantially change the physical and chemical properties of the fat .exclusive of those minor constituents which are capable of producing offflavors and olf-odors.

2. In a process of treating refined edible oils, fatty oils and fatty acids, by peroxidation and which treated materials are suitable after such peroxidation for use as bleaching agents in bread dough, except that they contain minor constituentswhich produce off-flavors and off-odors when suchj treated material has been incorporatedin bread dough as a bleaching agent and is subjected to baking conditions, as a pre-treatment to avoid the development of such olf-flavors and` ,oif'odors,'the step'which consists inV distributing Vthroughout a body of such refined edible fat possessing such constituents a material selected from the following halogens: chlorine, iodine, bromine, when chlorine is used the amount being from about 0.05 percent to about 1.00 percent, when iodine is used the amount being from'about 0.001 percent to about 0.002 percent, and when bromine is used the amount being about 0.01 percent, each being based on the weight of theV fat treated, the treatment being conducted with thorough mixing, so that the contact between thev halogen and the fat is such 'that the halogen acts on those constituents of thevfat which otherwise would produce oil-lievors and olf-odors, the amount of the halogen being insuiiicient to substantially change the physical 'and chemical properties of the fat exclusive of those minor constituents which are capablel of producing off-ilavors and off-odors.

743. AIn a process of treating refined edible oils, fatty oils and fatty acids, by peroxidation and which treatedmaterials are suitable after such peroxidation for use as bleaching agents in bread dough, except that they 4contain minor constituents which produce off-avors and olf-odors when such treated material has been incorporated in bread dough as a bleaching agent and is subjected to baking conditions, as a pre-treatment to'v avoid the development of `such offavors and olf-odors, the steps which consist in treating a body of such refined edible fat possessing such constituents with a material selected from the following halogens': chlorine, iodine, bromine, Awhen chlorine is used the amount being from about 0.05 percent to about 1.00 percent, when iodine is used the amount beingfrom about 0.001 percent to about 0.002 percent, and when bromine is lused the amount being about 0.014 percent, each being based on the weight of the fat treated, the treatment becon'tact between the halogen and the fat is such that the halogen acts 'on those constituents of the.' fat .which otherwise would produce offilavors and olf-odors, the amount of the halogen being insumcient to substantially change the physical and chemical properties of the fat exclusive of those minor constituents which are capable of producing olf-flavors and off-odors, mixing the fatty material and peroxidizing enzymes in the presenceof a gas containing free oxygen at a temperature between 32 F. and 140 F. to eiect a catalytic oxidation of the` fatty material, and separating the oxidized fatty material from the reaction mass.

44. In a process of treating rened edible oils, fatty oils and fatty acids, by peroxidation and which treated materials are suitable after such peroxidation for use as bleaching agents in bread dough, except that they contain minor constituents which produce oil-navors and oI-odors" and oiodors. the steps which consist in treating a; body of such refined edible fat possessing such constituents with a `material selected from the following halogens: chlorine, iodine, bromine,

when chlorine is used the amount being from l about 0.05 percent to about 1.00 percent, when iodine is used the amount being from about 0.001 percent to about 0.002 percent, and when bromine is used the amount being about 0.01 percent, each i being based on the weight of the 'fat treated..

the'treatment being conducted with thorough mixing, so that the contact between the halogen and the fat is such that the halogen acts on those constituents of the fat which otherwise would produce oif-avors and oifodors,-the amount of the halogen being insuiiicient to substantially change the physical and chemical properties of the fat exclusive of those minor constituents which are capable of producing oiI-ilavoi's and off-odors, mixing the fatty material and per. oxidizing enzymes in the presence of a gas containing free oxygen at antemperature between 32 F. and 140'F. to eiect a catalytic oxidation of the fatty material, and separating the oxidized fatty material from the reaction mass, mixing a solution of enzymes contained within and obtained from the living cells of yeast with the oxidized fatty material for a relatively short period at a temperature of about to50 lC. and separating the thus treated fatty material from the resulting mass.

5. In a process of treating refined edible oils,

' fatty oils and fatty acids, vby peroxidation and which treated materials are suitable after such 40,

peroxidation for usev as bleaching agents v in bread dough, except that they-contain minor constituents which produce oif-avors and oi!- odors when such treated material hasbeen incorporated in bread doughv as a bleaching agent and is subjected to baking conditions, as a pretreatment `to avoid the development of such oi!- avors and olf-odors, thesteps which consist iny passing liquid fatty material to be treated through a reaction zone at a constant predetermined rate while agitating the' material at high speed, introducing a halogen into the said zone at a constant predetermined rate under a prel determined head of liquid fatty material and' mixing the halogen with the fatty material while continuously withdrawing the treated material from the said zone, the halogen being selected those constituents of the fat which otherwisewould produce oi-avors and oil-odors, the

amount of the hangen being insumeient to sub.. 7

stantially change the physical and chemical properties of the fat exclusive of those minor constituents which are capable of producing oi!- flavors and` foff-odors.

6. In a vprocess of treating refined edible oils, fatty oils and fatty acids, by peroxidation in the presence of an extract containing peroxidizing enzymes obtained from unheat-treated soy flour `and which treated fatty materials are suitable after such peroxidation for .use as bleaching 'agents in bread dough, exceptthat they contain minor constituents which produce oiI-avors and olf-odors when such treated material has been incorporated in bread dough as a bleaching agent andis subjected to baking conditions, as a pre-treatment to 'avoid the development of lsuch olf-navors and oil-odors, the step which consists in treating a body of such refined edible fat possessing such constituents with av material selected from the following halogens: chlorine, iodine, bromine, whenV chlorine is usedthe amount. being from about 0.05 percent to about 1.00 percent, when iodine is used the amount being from about 0.001 percent to about 0.002 percent, and when bromine is used the amount being about 0.01 percent, each being based on the weight of the fat treated, the treatment being conducted with thorough mixing, so that the contact between the halogen and the fat is such that the halogen acts on those constituents of the fatwhich otherwise' would produce ofI-avors and o-cdors, the amount of the halogen being insuilicient to substantially change the. physical and chemical properties of the fat exclusive of those minorconstituentswhich are capable of producing oil-flavors and oil-odors.

7. In a 'process of treating refined edible oils. Y

fatty oils and fatty acids, by peroxidation in the presence of an extract containing peroxidizingA enzymes obtained from legumes containing peroxidizing enzymes and which treated fatty materials are suitable after such peroxidation for use as bleaching agents insbread dough, except that they contain minor constituents which pro duce ofi-flavors and off-odors when such treated material has been incorporated in bread dough as a bleaching agent and is subjected to baking conditions, as a pre-treatment to avoid the developm'ent of such ofi-liavors and off-odors, the step which consists in treating a body of such rened edible fat possessing such constituents with a material selected from the following halol l gens: chlorine, iodine, bromine, when chlorine change the physical and chemical properties o1A the fat exclusive of those minor constituents whichare capable of producing off-flavors and off-odors. 1

v HERBERT OI'I'ORENNER. 

